A novel mechanism for the fluxional behaviour of [Pd(η2-tetramethylethylenetetracarboxylate)(2-methylthiomethylpyridine)]

被引：22

作者：

Canovese, L

Lucchini, V

Santo, C

Visentin, F

Zambon, A

机构：

[1] Univ Venice, Dipartimento Sci Ambientali, I-30123 Venice, Italy

[2] Univ Venice, Dipartimento Chim, I-30123 Venice, Italy

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2002年 / 642卷 / 1-2期

关键词：

palladium-olefin complex; dynamic NMR; sulfur inversion mechanism; dimeric C-s intermediate mechanism;

D O I：

10.1016/S0022-328X(01)01197-4

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The fluxional behaviour of [Pd(eta(2)-tmetc)(N-SMe) (tmetc = tetramethylethylenetetracarboxylate, N-SMe = 2-methylthiomethylpyridine) in CD2Cl2 is governed by two mechanisms: (i) the concentration independent inversion at sulfur which averages the methylenic signals and collapses the four methyl signals of tmetc to two; (ii) the concentration dependent mechanism occurring via a dimeric intermediate with C-s symmetry which collapses the two residual tmetc signals into a singlet. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：58 / 63

页数：6

共 15 条

[1] PLATINUM METAL-COMPLEXES OF POTENTIALLY CHELATING ALKENE THIOETHER AND SELENOETHER LIGANDS - THE SYNTHESIS AND DYNAMIC NUCLEAR MAGNETIC RESONANCE STUDY OF [MX2(E[(CH2)NCR=CR2]2)] (M = PT OR PD - X = CL, BR, OR I - E = S OR SE - N = 2 OR 3 - R = H OR ME) AND THE X-RAY CRYSTAL-STRUCTURE OF CIS-DI-IODO-(5-THIANONA-1,8-DIENE)PLATINUM(II), [PTI2(S[(CH2)2CH=CH2]2)]P
ABEL, EW
EVANS, DG
KOE, JR
SIK, V
HURSTHOUSE, MB
BATES, PA
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (11): : 2315 - 2321
[2] ABEL EW, 1991, J CHEM SOC DA, P107
[3] THE KINETIC AND MECHANISTIC EVALUATION OF NMR-SPECTRA
BINSCH, G
KESSLER, H
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1980, 19 (06): : 411 - 428
[4] Palladium(0)-olefin complexes with potentially terdentate nitrogen-sulfur ligands. The role of the chelate in the olefin exchange path
Canovese, L
Visentin, F
Chessa, G
Gardenal, G
Uguagliati, P
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2001, 622 (1-2) : 155 - 165
[5] Synthesis, characterization and X-ray structural determination of palladium(0)-olefin complexes containing pyridin-thioethers as ancillary ligands. Equilibria and rates of olefin and ligand exchange
Canovese, L
Visentin, F
Chessa, G
Uguagliati, P
Dolmella, A
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 601 (01) : 1 - 15
[6] Equilibria and rates of olefin substitution in zerovalent palladium complexes containing a 2-pyridylmethanimine ligand
Canovese, L
Visentin, F
Uguagliati, P
Crociani, B
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (09): : 1921 - 1926
[7] Pregosin PS, 1996, COORDIN CHEM REV, V155, P35
[8] SCARTAZZINI R, 1967, TETRAHEDRON LETT, P2719
[9] Palladium(0) olefin complexes and enantioselective allylic amination/alkylation with a P,N-auxiliary
Selvakumar, K
Valentini, M
Wörle, M
Pregosin, PS
Albinati, A
[J]. ORGANOMETALLICS, 1999, 18 (07) : 1207 - 1215
[10] Catalytic and structural studies on complexes of a binaphthyl-phosphino-oxazoline auxiliary:: The meta dialkyl effect on enantioselectivity
Selvakumar, K
Valentini, M
Pregosin, PS
Albinati, A
Eisenträger, F
[J]. ORGANOMETALLICS, 2000, 19 (07) : 1299 - 1307

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